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Sorption of Organic Substances to Aquatic Solids

Sorption to Solids
Given the largest environmental compartments are the atmosphere, the hydrosphere, and the lithosphere, the soil/water and soil/air interfaces are equally important to the air/water interface. Processes that control the uptake of organic compounds by solids are extremely important in determining distribution in time and space, and this can be particularly important in determining transport velocities since solids are subject to different physical laws than water molecules. For the most part, the solids of significance to understanding sorption are small clay particles which may be partially coated with natural organic matter. The aquatic environment is normally considered to consist of three phases: water, settleable particles, and non-settleable particles (sometimes referred to as colloids). The significance of sorption is profound. Sorption influences many exchange processes, such as air/water exchange, because it affects the freely dissolved concentrations of organic compounds in natural systems. Only the freely dissolved compounds are subject to exchange processes across interfaces other than sorption. This could have a dramatic effect on volatilization rates for example is the compound was extremely sorptive to aquatic particles because the solid-bound fraction is not free to move across the air/water interface. Sorption is normally modeled as an equilibrium process between dissolved solutes (in air or water) and solid-associated solutes.

I. TERMS A. Adsorption - The interphase accumulation or concentration of substance at a surface or interface. Concentration in boundary region is greater than in the interior or contiguous phase. Absorption - The accumulation of substance whereby the concentration is evenly distributed throughout the contiguous phase. Sorption - General expression of the process of adsorption or absorption without specifying the mechanism of interphase transfer. The material being sorbed is the sorbate, and the sorbing phase is termed the sorbent. Sediment - Fragmented geological material that originates from the disintegration of rocks and is transported by, or suspended in, or deposited by air or water or is accumulated in beds by
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B.

C.

D.

other natural processes. Normally classified as bed sediments (sedimented particles) or suspended sediments (suspended in water) in aquatic systems. E. Colloid - dispersion of particles of one substance (the dispersed phase) throughout another substance or solution (continuous phase). Particle sizes range from ~1 m to 1 nm.

II. Sediment Lithology 1. Geologic materials are derived from silicate rocks. Silicates make up ~90% of the minerals in the earth's crust. Bedrock may be in the form of igneous, metamorphic, or sedimentary in origin. 2. Bedrock is subject to physical and chemical weathering processes. Reaction and fragmentation produces soils and sediments. Weathering reactions also form dissolved phase ions is natural waters. The general reaction scheme for chemical weathering is as follows: bedrock + atmospheric input altered rock (clays) + ions 3. Clays are fine-grained, hydrous, silicates derived from bedrock. Primary elemental composition is O, Si, and Al. Clay structure is closed-packed sheets of O atoms with Si and Al ions in interstitial spaces. O atoms arranged in a tetrahedral layer on top of an octahedral layer.

III. Organic Geochemistry

low MW acids , 25%

pollutants, 5%

humic & fulvic acids, 50% neutrals and bases, 20%

A. All natural waters contain organic matter; the major fraction of organic material is in the form of humic and fulvic acids (~50% of OM); contaminants and pollutants are <5% (and typically much lower) B. Important terms: 1. DOM/DOC - dissolved organic matter/carbon; material which passes through a 0.45 m filter (operationally defined). 2. POM/POC/SOM/SOC - particulate organicmatter/carbon; suspended organic matter/carbon; material retained on a 0.45 m filter. 3. TOC - total organic carbon; sum of POC + DOC. 4. VOC - volatile organic carbon; organics trapped from a water sample by stripping techniques.

5. COM - colloidal organic matter; ranges in size from 0.45 m to 1 nm in spherical diameter; difficult to measure and seldom used term, but extremely important in geochemical processing. 6. allochthonous - terrestrial sources outside of aquatic system; streams and rivers 7. autochthonous - sources within an aquatic system (e.g., algae and microbs); large lakes, estuaries, and oceans DOC varies according to water source: range is seawater (lowest) to bogs (highest); average values are shown below Bog water River water Precipitation Sea water 33 mg/L 7 mg/L 1 mg/L 0.5 mg/L

C. Aquatic Humic Substances (AHS) - high molecular weight, refractory, yellow-black, amorphous, macromolecular acids which show appreciable solubility in water. 1. Fulvic acids - AHS which range from 500 - 2,000 amu; corresponds to 80-90% of the AHS fraction; yellow in color. Soluble in water at pH <2. 2. Humic acids - AHS which range from 2,000 - 100,000 amu; commonly associated with clay minerals and Fe/Mn oxyhyroxides; corresponds to 10% of AHS fraction; HS's precipitate from water at pH <2. 3. Humin - humic substances found in soil that is insoluble in water; very high molecular weight.

4. AHS play role in the (a) chemical weathering processes, (b) pollutant transport; (c) regulating acidity of natural waters. D. Sources and origin of organic matter -- vegetation largest C source 1. soils - soils are large sources of org. matter; the extent depends on vegetation present; prairie>forest>arid soil show order of OM runoff; prairie has much non-woody OM in soil; organics flushed to streams with precipitation. (Figure below adopted from Leenheer, J. et al. 1995.
Environ. Sci. Technol. 29, 399.)

1. leaching of plant material into water 2. leaching of plant material through soil with biochemical modification 3. leaching of soil humic substances into water d. lysis of algal cells with photochemical modification e. UV oxidation of surface active OM followed by polymerization reactions 2. Humus formation theories a. lignin breakdown with byproduct polymerization b. cellulose dehydration, oxidation, and polymerization c. lignin fragmentation d. condensation of sugars and amino acids

3. Chemical Characterization. With amorphous structure, no definitive structure possible. Characterized by presence of important functional groups on AHS Because the structure of DOC is so complex and variable, it is often described in terms of functionality present. Acidic groups 1. Carboxyl group: -COOH. The carboxyl group ionizes -COOH + H2O H3O+ + -COOThe pKa for carboxyl groups is ~4-7. In surface water, carboxylate ion predominates. Carboxylate ion profoundly increases water solubility. ~ 1 carboxyl group per every 7 carbon atoms in AHS. 2. Enol group: -C=C(OH)-. pKa varies from 6 to 9. Often ionize in natural water. 3. Phenol group: Ar-OH. Phenol has pKa of 9; electron withdrawing groups increase Ka and make more acidic, e.g., Cl, -NO2. Neutral groups 1. Hydroxyl group: -OH. pKa is 14 and does not ionize but does increase water solubility by forming H-bonds with water. 2. Ether group: -C-O-C-. Increases water solubility slightly; is present a 1 per every 30 C atoms. 3. Aldehyde group: -C(=O)H and ketone group -C(=O)- Increases water solubility.
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4. Ester group: -C(=O)-O-C. Formed from carboxylic acids; increases water solubility. Basic groups 1. Amine group: -NH2. Amines are proton acceptors and form cations in neutral water: -NH2 + H2O H3O+ + -NH3+ Also form hydrogen bonds. Amine groups greatly increase water solubility. Relative solubility of different functional groups shows importance of carboxyl group in enhancing solubility. Implications of AHS AHS play a role in the mobilization, transport, segregation, and deposition of trace metals in soils and sediments Play a key role in the weathering of rocks an minerals Transport metals in natural waters Can reduce oxidized forms of certain metal ions Can affect bioavailability of metal ions

Example AHS binding reactions with metal ions in solution


O C OH 2+ + M + H2O O C O
2+

O C OMOH + O H
+

+ M OH O C O
-

O O M

+ H+

O O + M
2+ +

C OH O O
-

M + H O O O
-

C O + M (H2O) OH
2+

C O H O H OH

2+

For organic pollutants, AHS enhances their solubility in water

IV. SORPTION ISOTHERMS FOR SOILS AND SEDIMENTS Sorption of quantified and evaluated by fitting sorption data to one of several models. The three most widely used sorption models which include the Langmuir isotherm, the Freundlich isotherm, and the BET isotherm. All three isotherms describe sorption as a dynamic equilibrium established for an organic compound (often referred to as the sorbate) between the sorbent and the solvent. The features of each model are described below.

A. Langmuir Isotherm

Cs = Cs(sat)KLCw/(1 + KLCw)

(1)

Cs = Concentration of chemical in solid material (mg/kg) Cs(sat) = monolayer saturation concentration of solid material (mg/kg) KL = constant related to binding energy of sorbate to sorbent surface (Temp dependent) (L/mg) Cw = concentration of chemical in water (mg/L) Langmuir Model Assumptions: a. sorbent has fixed "number" of sites (saturable) b. all sites have equal binding enthalpies independent of the extent of coverage c. maximum sorption is a monolayer on surface of substrate

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Langmuir Isotherm 1 Cs, mg/kg 0.8 0.6 0.4 0.2 0 0 0.05 0.1 Cw, mg/L
Figure 1. Langmuir isotherm: Cs(max) = 850; KL = 0.15

Saturated Region Non-linear Region

Linear Region

0.15

0.2

Linear form of Langmuir equation is given as:

1/Cs = 1/Cs(max) + 1/( Cs(max) KLCw)

(2)

The Langmuir isotherm works best for process such as ion or ligand exchange. The sorbents tend to be mineral in nature, with a fixed number of active (binding) sites. Note the saturation of the sorbent at high concentrations of solute in the water phase. For the linear region of the Langmuir curve, can define distribution constant Kd = Cs(max)KL, Kd = Cs/Cw at equilibrium

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B. BET isotherm

P/[V(Po - P)] = 1/VmC + (C-1)/VmC(P/Po)

(3)

P = equilibrium pressure of sorbate, atm V = volume of gaseous sorbate sorbed, L Po = liquefaction or saturation pressure of sorbate, atm Vm = volume of gaseous sorbate sorbed when the entire surface is covered with a complete monolayer C = constant related to heat of sorption The BET isotherm has been used to study the sorption of organic compounds, such as pesticides, with relatively high vapor pressures, especially when the interaction occurs on mineral surfaces. BET Model Assumptions: a. related to Langmiur except that sorption may occur at multiple layers b. each layer is modeled by Langmuir isotherm c. second layer may form before first is saturated d. sorption occurs at fixed sorption sites C. Freundlich isotherm This is an empirically derived model, and has limited theoretical foundation

Cs = KFCwn
KF = Freundlich distribution constant (L/kg) n = exponential term of water concentration

(4)

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Freundlich Isotherm 250 200 Cs, mg/kg 150 100 50 0 0 0.05 0.1 Cw, mg/L 0.15 0.2

Figure 2. Freundlich isotherm: Kd = 1000; n = 0.85

The linear form of Freundlich is

log Cs = log KF + n logCw

(5)

The mechanism of sorption is mixed between fixed sites and a pseudopartition process; many layers of fixed sites exist all with different enthaplies (?????); no mechanism can be deduced from this relation. The Fruendlich isotherm is an emperical relation.

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D. Linear isotherm Specialized case of Langmuir and Freundlich (n = 1) isotherms

Cs = KdCw

(6)

This model is consistent with a partitioning mechanism for sorption. The solute is homogeneously distributed throughout each phase.

Linear Isotherm 200 Cs, mg/kg 150 100 50 0 0 0.05 0.1 Cw, mg/L 0.15 0.2

Figure 3. Linear isotherm: Kd = 1000.

The linear isotherm is most commonly used to determine empiricallyderived distribution constants. Linear isotherm works best for chemicals with very low water solubilities (e.g., HOCs)

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E. Distributed sorption models In many cases a single sorption model is not adequate to completely describe the sorption behavior of organic solutes across all concentration ranges observed in nature. A mixture of models may be applied, referred to as distributed reactivity models. The simplest cases involve a combination of two sorption mechanisms such as 1. Linear and Fruendlich

Cs = KdCw + KFCwn
2. Linear and Langmuir

(7)

Cs = KdCw + (Cs(max)KLCw)/(1 + KLCw)


Simple distributed models work best when mixed mechanisms are involved in sorption, such as OM partitioning and mineral, site-

(8)

F. Organic carbon normalized sorption constants, Koc 1. It has been shown that organic substances are more enriched in solids with higher organic carbon contents. 2. Sorption constants are often normalized to the amount of organic carbon in the solid phase as:

Koc = Kd/foc Koc = Coc/Cw


foc = weight fraction (g/g) of organic carbon in solid phase
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(9) (10)

Coc = concentration of chemical in solid phase (mg/kg) normalized to oc content (e.g., Cs/foc) Cw = concentration of chemical in water (e.g., mg/L) Nonlinearity is often observed in experimental Koc determinations, but usually at relatively high concentrations of Cw. From eq 8 above Coc = KocCw Isotherms between Coc and Cw for organic chemicals appear linear up to the region of Coc (kg/kg) = KocCw = 0.01, above which isotherms show non-linearity. Reduction of Koc is thought to be due to saturation by the HOCs of natural organic matter in the solids. Less binding sites are available at relatively high Coc values. G. Sorption partitioning theory. Sediment organic matter behaves as organic sovent (octanol). Treat sorption as partitioning process.

Ci,wvwi,w = Ci,ovo i,o

(11)

Ci = concentration of ith compound in water (w) or organic matter (o) (mol/L) v = molar volume of water (w) or organic matter (o) (L/mol) = activity coefficient of compound in water (w) and org. matter (o)

Koc = Ci,o/Ci,w = vwi,w /voi,oo log Koc = - log Si,w - log vo - log i,o - log o log Koc = - log Si,w - log (voo)

(12) (13) (14)

o = bulk density of organic matter (kg/L) (and assuming i,w >> i,o)

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G. Sorption variables 1. Temperature - like partitioning theory, as temperature inceases sorption decreases because Hs is negative. 2. Total suspended matter concentrations (TSM) - as TSM increases sorption decreases. Colloidal materials are released from particles which enhance the solubility of dissolved phase solutes. 3. pH - for ionizable solutes, sorption is very pH dependent. Typically, the neutral form is the most sorptive. As the fraction of the ionic form increases sorption decreases.

V. MASS FRACTIONATION Organic chemicals in the aquatic environment distribute between water and solids according to thermodynamic principles and geochemical parameters A. Liquid to solid ratio. The effects of the liquid-solid ratio in defining the distribution of organics between sediments and water

w = CwVw/(CwVw + CsMs)

(15)

w = mass fraction (g of chemical in water/g of chemical in water and solids) of compound in water phase C = concentration of chemical in water (w) or solid (s) phases (mol/L and mol/kg, respectively) Vw = volume of water in system (L) Ms = Mass of suspended sediment (kg) per unit volume of water (Vw) Note that as Cs and TSM increase, w decreases
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Cs = KdCw
Substitution of eq 16 into eq 15 yields

(16)

w = CwVw/(CwVw + CwKdMs) w = Vw/(Vw + KdMs)

(17) (18)

For surface water systems, the following relation is useful (dividing eq 18 through by Vw) for a system consisting of water and particles

w = (1 + Kd[TSM])-1
and thus,

(19)

p = 1 - w

(p = mass fraction in particles)

(20)

For groundwater systems, the following form of above eq is useful

w = {1 + Kd[s(1 - )/]}-1
s = bulk density of solid (kg/L) = porosity of system (volume water/total volume) B. Mass balance relations and fractional composition - 3 phase model 1. Introducing colloids Colloids are small particles in size range of 1 m to 1 nm; colloids cannot be efficiently filtered from water like suspended sediments

(21)

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2. Colloid composition: a. b. c. d. Clay minerals Oxyhydroxides of Fe and Mn Humic and fulvic acids in water Very small microorgams (e.g., viruses)

Colloids can play important role in sorption of organic substances from water, esp. those with substantial OM (i.e., foc). 3. Colloids comprise some of dissolved organic carbon (DOC) fraction in natural waters 4. Colloid sorption can be described much like that for sediments:

Kdoc = Cdoc/CW
Kdoc can be estimated via Kow or Sw using available LFERs 5. Effect of presence of colloids in natural waters

(22)

i. Apparent Kp's (TSP) tend to decrease when DOC increases. ii. Very hydrophobic Koc's tend to be overestimated in natural waters when using Kow as estimator iii. Colloids enhance water solubility of hydrophobic organics, thereby increasing amount in apparent dissolved phase. Fractional Composition of Organics in Water: 3 phase system model

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Mass balance can be expressed by the following equation, stating that the organic compound is distributed between dissolved, particulate, and colloidal phases

Ct = Cw + Cp + Cc

(23)

C = phase concentration, dissolved (w), particulate (p), and colloidal (c), mg/L [TSM] = total suspended matter concentration (use kg/L as unit) [DOC] = dissolved organic carbon concentration (use kg/L as unit) Kd = mass based particle-water distribution constant, L/kg Kdoc = DOC/water partition coefficient, L/kg ( Koc) foc = fraction of organic carbon in particulate phase (g/g)

Ct = Cw + Cw[TSM]Kd + Cw[DOC]Kdoc

(24)

a. fractional mass distribution in the dissolved phase, w

w = (1 + [TSM]Kd + [DOC]Kdoc)-1

(25)

b. fractional mass distribution in the particulate phase, p

p = (1 + 1/([TSM]Kd) + ([DOC]Kdoc)/([TSM]Kd))-1
c. fractional distribution in the colloidal phase, c

(26)

c =(1 + ([TSM]Kd)/([DOC]Kdoc) + 1/([DOC]Kdoc))-1

(27)

in most applications, the following substitution is made in the above eqs for particle phase concentrations Kocfoc = Kd

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Note that w + p + c = 1
6. Correction of field measured distribution constants Field studies that measure particle/water distribution constants typically assume that Kd fits a linear isotherm (measured values are typically <1 ppb), thus
meas = Kd

Cp Cw

the measured (meas) Cw includes both truly dissolved and colloidal fractions using most analytical methods; need to mathematically correct for amount in colloids to derive actual (act) Kd; the measured Kd is dependent on amount of chemical associated with colloids
meas Kd

(Cw + Cc )

Cp

1 1 (1 + K doc [ DOC ]) act Kd

(28)

Rearranging for the actual Kd yields


act meas (1 + K doc [ DOC ]) Kd = Kd

Typical values of DOC run from 0.5 mg/L (estuarine) to 10 mg/L (riverine); the Kdoc term in the above eq becomes important when Kdoc values approach thresholds

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For example, for the multiplier of (1+ Kdoc[DOC]) to be >5, the following apply DOC, mg/L Kdoc 0.5 >8 x 106 5 >8 x 105 10 >8 x 104 Assuming Kdoc = 0.41Kow Log Kow >7.29 >6.29 >5.29

Only very hydrophobic organic contaminants will be substantially affected by DOC in most surface water environments VI. SORPTION OF ORGANIC VAPORS TO SOILS Vapors of organic compounds sorb to soils. The sorption is modeled as shown above using BET isotherms. The magnitude of sorption depends on (a) temperature and (b) relative humidity. Since soils are mineral in nature and represent polar surfaces, water binds very tightly to the surface of soil particles. Dry soil is an effective sorbent for organic vapors. Sorption coefficients for vapor phase organic substances are generally modeled by the following process model:

ln K = A + B/T

(26)

This model is a form of the vant Hoff equation, and the constant B is defined as the heat of sorption of the vapors to the solids. The moisture content of the soil is extremely important in determining the degree of sorption. You may have noticed the fresh smell in the air after in rains. This is due to the release of sorbed plant (green leaf) volatiles from dry soil after rainfall. Dry soil is important is the vadose

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zone of ground water and for the uptake of air phase organic substances from the atmosphere.

VII. LINEAR FREE ENERGY RELATIONSHIPS Correlations between sorption and Sw,liq and Kow are routinely performed. The rules governing estimations of Koc from physical properties of organic compounds are similar to that described for octanol/water partition coefficients. Examples of LEFRs for the sorption of hydrophobic organic compounds is shown below .

Correlations with reference state water solubility log Kom = -0.93 log Si,w.liq - 0.17 (aromatic hydrocarbons) log Kom = -0.56 log Si,w.liq + 0.97 (phenyl ureas) log Kom = -0.70 log Si,w.liq + 0.35 (chlorinated hydrocarbons) Correlations with octanol/water partition coefficients log Kom = 0.88 log Kow - 0.27 (chlorinated hydrocarbons) log Kom = 0.81 log Kow - 0.25 (chlorophenols) log Kom = 1.12 log Kow + 0.15 (phenyl ureas) log Kom = 1.01 log Kow - 0.72 (aromatic hydrocarbons)

VIII. SORPTION KINETICS A. Desorption of organic pollutants from sediments shows a kinetic hysteresis effect for aged sediments. This is not observed for recently spiked sediments.

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B. Sediments behave as aggregates which have macropores and micropores. C. Aging allows greater pollutant diffusion into aggregate micropores, which is diffuses out of sediment phase very slowly. D. Aging theories i. Micro- and macropores in the mineral fraction of sediments trap HOCs in the micropores. ii. Natural organic matter (NOM) shows two domains. One domain is labile and shows reversible sorption kinetics. This labile fraction is thought to behave as a gel phase, and chemically is composed of predominantly aliphatic carbon. The gel phase is highly fluid and allows easy access to HOCs. The second domain is characterized as more crystalline, and is chemically is enriched in aromatic carbon and is more highly cross-linked. This second domain shows some level of irreversible sorption kinetics, and accounts for the slow desorption kinetics observed in aged sediments. The aromatic enriched carbon is the product of sediment diagenesis, where organic matter is altered by microorganism during sediment aging. iii. Soot carbon. The aerosols produced from C combustion contain condensed soot carbon highly enriched in aromatic rings. Soot carbon is thought to be crystalline-like, and appears to sequester HOCs to various extents. Soot carbon clearly shows enhanced sorptive capacity relative to natural organic matter.

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Sample Problems: 1. What are the major sorption isotherms used to characterize the sorption of organic substances to solids? How can you differentiate each one through a linear plot? Answer: Linear, Freundlich and Langmuir isotherms. Though inspection of axis labels, type of isotherm can be identified For example: linear plots results as linear, Cs vs. Cw; Fruendlish is log Cs vs. log Cw; and Langmuir is 1/Cs vs. 1/Cw

2. A Freundlich isotherm yields the linear equation below for the sorption of compound Z to Potomac River sediments. What is the Kd for compound Z? If the foc of Potomac River sediment is 0.14, what is the Koc for Z? log Cs = 0.92 log Cw + 3.69 Answer: According the Fruendlich equation, 3.69 = log Kd; Kd = 4,900 L/kg (note units). Koc = Kd/foc = 4,900/0.14 = 35,000 L/kg. 3. A 44.5 L sample of Potomac River water was collected and analyzed for the organochlorine pesticide lindane (-hexachlorocyclohexane) in the dissolved and particulate phases. The volume based (i.e., mass/volume) concentrations were found to be 16 ng/L in the dissolved phase and 9.9 ng/L in the particulate phase. The total suspended matter (TSM) in Potomac River water was 29.7 mg/L, and the suspended organic carbon (SOC) was 3.6 mg/L (a) What is the fraction of lindane in the dissolved phase of river water? (b) What is the mass based (mass/mass) concentration of
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lindane in the particle phase? (c) Estimate the Kd and Koc of lindane in Potomac River sediments. Answer: (a) the mass fraction of lindane in the dissolved phase is (make sure units are similar for all measurements) w = Cw/(Cs + Cw) = 16 ng/L/(16 ng/L + 9.9 ng/L) = 0.62 = 62% (b) Cs (mass based conc) = (Cp (volume based conc)/[TSM]) x A (unit constant)) = (9.9 ng/L/29.7 mg/L) x 1000 mg/g = 330 ng/g (c) Cs = Kd Cw and Kd = Cs/Cw (assuming Kd is constant)

= 333 ng/g/16 ng/L x 1000 g/kg = 20,800 L/kg Koc = Kd/foc = Kd/(SOC/TSM) = 20,800/(3.5/29.7) = 176,500 L/kg

4. The concentrations of benzyl-n-butyl phthalate (BBP, a plasticizer) in river water ([TSP] = 22.9 mg/L; foc = 0.16; [DOC] = 4.6 mg/L) are 1.9 ng/L and 0.89 ng/L in the "dissolved" (Cd) and particulate phases (Cp), respectively. Estimate the Kd for BBP using a 3-phase model that corrects for binding to colloids. (a). Cp =
wCdKd[TSM]

(where Cd = Cw + Cc)

Thus, Kd = Cp/(
w

wCd[TSM])

= (1 + Kdoc[DOC])-1 for colloids and water

Must estimate Kdoc as 0.41(Kow) = 0.41(104.91) = 33,326 L/kg

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Kd = Koc foc Kd = Cp/[(1 + Kdoc[DOC])-1 (Cd [TSP])] = 0.89 ng/L/[(1 + 33,326 L/kg x (4.6 x 10-6 kg/L))-1 (1.9 ng/L x (2.29 x 10-5 kg/L)] = 2.36 x 104 L/kg

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Gas/Particle Partitioning

Aerosol

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The Atmosphere and Gas/Particle Partitioning


The atmosphere is a major pathway for the transport and deposition of natural and anthropogenic organic chemicals, including pollutants. Vast quantities of organic contaminants are released into the atmosphere, either directly or indirectly, from a variety of sources. For example, many field-applied agricultural pesticides volatilize directly into the atmosphere or, after attatching to soil material, are blown into the air by the winds. Polycyclic aromatic hydrocarbons (PAH), are emitted into the atmosphere by automobiles, forest fires and many other combustion sources. Polychlorinated biphenyls (PCBs) are released from leaking old electrical tranformers and landfills into the air. Once airborne, stable chemicals such as PCBs can be transported thousands of kilometers from their original sources, contaminating even remote regions of the earth. For example, PCBs and a large number of organochlorine compounds like DDT and chlordane insecticides have been detected in air, water, and biota over the open oceans, in Antarctica and the Arctic, all regions well removed from possible sources of the pollutants {see for example Bidleman et al., 1989}. A complete assestment of total inputs of organic pollutants into an aquatic environment must therefore consider contributions from atmospheric depositional processes.

I. Aerial Distribution And Removal Of Trace Organics Semivolatile organic pollutants are found in the atmosphere in the gas [vapor] phase (G) or associated with particles (P).

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Theory suggests that the distribution of SOCs between the gas (G) and particle (P) phases depends on several factors including: 1) particle size distribution 2) particle surface area 3) organic content of particles 4) vapor pressure of the SOCs 5) the functional groups of a SOCs are also likely important for polar compounds, since they can possibly undergo chemical adsorption, in addition to physical adsorption and absorption. Before proceeding with our discussion of gas-particle distributions of semivolatile organic compounds, let's consider several other important aspects of atmospheric chemistry. II. ATMOSPHERIC COMPOSITION AND CHEMISTRY Atmospheric Gases The atmosphere is composed primarily of two dominant gases nitrogen and oxygen, with much lesser amounts of other gases (see table below from Seinfeld, 1986). Although the concentrations of the gases has remained remarkably stable over time, the atmosphere is really a dynamic system, with the gases constantly being exchanged with the oceans, vegetation, and other biological organisms. Measurable organic pollutant atmospheric concentrations usually range from femtogram per cubic meter of air (fg/m3) up to g/m3.

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Atmospheric Gases Gas Ar Ne Kr Xe N2 O2 CH4 CO2 CO H2 N2O Avg. Conc., ppm 9340 18 1.1 0.09 780,840 209,460 1.65 332 0.05-0.2 0.58 0.33 Approximate Residence Time ? ? ? ? 106 years 10 years 7 years 15 years 65 days 10 years 10 years

III. ATMOSPHERIC PARTICLES Aerosols in the atmosphere have several important implications: 1. Pose a human health hazard at high concentrations and size distributions 2. Scatter and absorb visible radiation, thus altering visibility; can alter earths climate 3. Provide particles in the atmosphere where important reactions and interactions can occur Aerosols originate from 1. condensation of atmospheric gases
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2. wind action on the earths surface A. Fine aerosol are those with mass median diameters (D) < 2 m, originate predominantly from the condensation of precursor gases in the atmosphere Subdivided into two size fractions 1) Ultrafine aerosols (D = 0.002 to 0.02 m) which arise from gasto-particle conversions and some combustion processes. Lifetimes are short (often minutes) due to rapid coagulation and condensation forming. 2) Fine aerosols (D = 0.02m to 2 m). Arise from condensation of ultrafine aerosols. Aerosols rarely grow to larger than 2 m because they are too large to grow by condensation and coagulation. This fraction is also called accumulation mode because there particle size is stable in the atmosphere. a) Because of the nature of their source, these small particles generally contain far more organics than coarse particles. b) Represent a small portion of the total particle number (e.g., 5%) but a significant portion (e.g., 50%) of the aerosol mass. c) Too small to settle out rapidly - longer atmospheric lifetimes than coarse particles. d) Removed relatively slowly by incorporation into cloud droplets followed by rainout, or by washout (scavenged by falling raindrops) during precipitation. OR by dry deposition to surfaces by eddy diffusion or advection. 3) Coarse particles (D > 2 m) produced mostly by mechanical processes such as grinding, wind, or erosion. a) Major deposition processes are gravitational settling and washout by precipitation.
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b) Can be transported long distances by convective processes. c) Usually predominantly inorganic in composition. d) Most biological particles (pollen, spores, etc.) are in the coarse range.

IV. Gas-Particle Partitioning Of SOCs The distribution of airborne organic compounds between the Gas (G) and Particle (P) phases is really only important for SOC, since compounds classified as volatile (VOC) or nonvolatile (NOC) are typically found entirely in the gas or particle-associated phases, respectively. A. SOC bound to atmospheric particles consist of: 1) Nonexchangeable fraction, which is strongly adsorbed to active sites or embedded in the particle matrix and not in equilibrium with its gas phase. {Some polar organics may predominately experience irreversible chemical adsorption and never be available for exchange. Little work has been done to look at the phase distributions of polar organics in the atmosphere.} 2) Exchangeable fraction, which is more loosely bound and controlled by the SOC gas-phase concentration (vapor pressure!) in the air.

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Sorption Models Junge-Pankow Adsorption Model p = c/(fR + c) where: p = Cp/(Cg + Cp) (2) (1)

p = the fraction of particle-bound SOC Cp, Cg = concentration of chemical in particle and gas phase (ng/m3 air) FR = solute reference fugacity (liquid phase vapor pressure) = the average total particle surface area per volume of air (cm2/cm3) -7 ( ranges from ca. 4.2 x 10 for clean continental background to -5 3.5 x 10-6 for rural air to 1.1 x 10 for urban air.) c = term that depends on SOC molecular weight, particle surface concentration for monolayer coverage, and the difference between the heat of desorption from the particle surface and the heat of vaporization of the sorbate. (Junge assumed c = 0.13 torr-cm 17.2 Pa-cm = 1.7 x 10-4 atm-cm, depending on pressure units.) also, eq. 2 can be expressed as p = Cp[TSP]/(Cg + Cp[TSP]) CP = concentration in particle phase (ng/g particles) Cg = concentration of chemical in gas phase (ng/m3 air) TSP = total suspended particulate concentration (g/m3) The particle-gas partition coefficient may be introduced into the fractional distributional equations as Divide rhs of eq 3 by Cg
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(3)

p = Kp[TSP]/(1 + Kp[TSP]) Kp = particle-gas partition coefficient Kp = Cp/Cg CP = concentration in particle phase (ng/g particles) Cg = concentration of chemical in gas phase (ng/m3 air)

(4)

(5)

Equation 4 may be used to predict , which can be used for atmospheric transport and deposition modeling. The Junge-Pankow model and eq 1 assume physical adsorption only, since this equation was derived using Langmuir isotherm assumptions. Combining eq 1 and 5: log Kp = log (c/[TSP]) - log fR (6)

A plot of log Kp vs. log fR has a theoretical slope of 1 and an intercept related to the particle specific surface area. Problems associated with the adsorption model include difficulties in measuring and Atsp, and uncertainties in the parameter c. Slopes often differ from 1 because of sampling artifacts, non-equilibrium effects, or thermodynamic factors Kp (m3/g) is a partitioning constant, TSP is the total suspended particle concentration (g/m3), and F (ng/m3) and A (ng/m3) are the operationally defined particulate-associated and gaseous concentrations of the compound of interest, respectively. Blow-off loses or adsorption gains to the filter may occur biasing the ratio. Despite artifact problems, measurements of A, F and TSP have been used to estimate the G/P distribution (using Kp) of nonpolar SOC and the factors controlling it.

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Octanol-Air Partition Coefficient (Koa) Model This model assumes partitioning between gas phase and liquid-like film on particles that can be modeled using Koa. Kp = 10-9Koafom(Moct/Mom)(oct/om)/g where: Koa = Co/CA , ratio of SOC conc. at equil. in octanol and air (dimensionless). fom = fraction of particle organic matter (wt/wt) Moct = molecular weight of octanol Mom = molecular weight of particle organic matter oct = activity coefficient of SOC in octanol. om = activity coefficient of SOC in particle organic matter film. g = density of octanol (820 kg/ m3) Assuming similar molecular weights for octanol and the particle organic matter, then (oct/om) 1 Kp = 1.2 x 10-12Koafom(Moct/Mom) or in log-log form: Log Kp = log Koa + log fom + log (Moct/Mom) 11.92 (9) (8) (7)

Plot of log Kp vs. log Koa has a theoretical slope of +1 and an intercept related to the absorbing properties of the aerosol. The molecular weight ratio is often dropped because it contributes very little in magnitude to the constant, providing

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Log Kp = log Koa + log fom 11.92 Koa can be measured directly, or it can be estimated as Koa = Kow/ KAW

(10)

(11)

the ratio of the octanol-water partition coefficient to the dimensionless Henrys law constant. Koa is considered to be more reliably determined (or estimated) than is the fR of a compound that is a solid at ambient temperatures.

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Sample Problems 1. If 42% of an organic chemical is associated with atmospheric aerosols, calculate the particle-gas partition coefficient of the chemical given an air TSP of 29.1 g/m3. Answer: the distribution of chemicals in air may be estimated using the Junge-Pankow model as p = Kp[TSP]/(1 + Kp[TSP]) solving for Kp yields Kp = p/{(1-p)[TSP]} = 0.42/(0.58 x 29.1 g/m3) = 0.026 m3/g

2. Estimate the particle mass fraction of PCB 194 in Fairfax City air, with a TSP of 88.3 g/m3 (fom = 4.1%) at 25 oC separately using the Junge-Pankow model and the Koa model. Answer: PCB 194 properties are as follows: Po = 1.61 x 10-10 atm Tf = 158 oC = 431 K PoL = exp(ln 1.61 x 10-10 atm + 6.74(431 K/298 K -1)) = 3.26 x 10-9 atm Sw = 0.0002 mg/L = 4.65 x 10-10 mol/L Kow = 107.67 KH = 1.61 x 10-10 atm/4.65 x 10-10 mol/L = 0.346 atm-L/mol

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Junge-Pankow Model` Log Kp = log p = log (c/[TSP]) - log fR = log{[(1.7 x 10-4 cm2/cm3) (1.1 x 10-5 atm-cm)]/ 88.3 g/m3} - log (3.26 x 10-9 atm) = -10.67 - (-8.49) = -2.18 m3/g Kp = 0.006558 m3/g p = Kp[TSP]/(Kp[TSP] + 1) = 0.006558(88.3)/(0.006558(88.3) + 1) = 0.37 Koa Model Log Kp = log Koa + log fom - 11.92 Koa = Kow/Kaw = 107.67/(0.346 L-atm/mol/(0.0821 L-atm/mol-K x 298 K)) = 3.31 x 109 log Kp = 9.52 + log (4.1) - 11.92 = -1.79 Kp = 0.01632 m3/g p = Kp[TSP]/(Kp[TSP] + 1) = 0.01632(88.3)/(0.01632(88.3) + 1) = 0.59 The two models provide somewhat different results.

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